Carboxy polymethylene guanamines



I fiacilitate the reaction.

Patented Sept. 9, 1947 CARBOXY POLYMETHYLENE GUANAMINES Jack Theo Thurston, Cos Cob, Conn, assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine N Drawing. Application August 30, 1941, Serial No. 409,131

4 Claims. (Cl. 260-2495) This invention relates to guanamines in which the Z-carbon atom of the 4,6-diamino-1,3,5-triazinering contains as the substituent group a carboxy polymethylene radical which may be either a straight chain or an alicyclic ring.

The guanamines of the present invention are of particular significance as they react with formaldehyde to form resins which are soluble in aqueous alkaline media and can be applied as textile finishes which on curing by heat are transformed from a water-soluble to a water-insoluble form and when incorporated with other aldehyde resin-forming compounds having hydrophobic groups, they serve as water-repellents for textiles and paper. An important characteristic of these finishes is that the water-repellency is effected without objectionable stiffening of the goods. In other words, the finish does not form a continuous film from fiber to fiber.

The products of the present invention can be produced by various methods and the invention is not limited to any particular method of preparation. Two processes are, however, preferred because of their simplicity and. cheapness. In one process a dibasic acid ester is combined with 2 good solvents for biguanide. The cheap mono- .h'ydric paraflin alcohols such as methanol and ethanol operate well and are of particular advantage because the most readily available esters of the carboxylic acids are usually the methyl and ethyl esters, and if the alcohol which is used as a solvent corresponds to the alcohol radical of the ester, no separation problem arises. Excellent results are, however, obtained with the lower monohydric alcohols such as the ether alcohols, for example, the ethyl ether of ethylene glycol.

The invention will be described in greater detail in conjunction with the following specific extwo moles of a biguanide, preferably in a solvent,

amples which are typical illustrations. The parts are by weight.

Example 1 Malonoguanamine N II II and Garboxyacetoguanamine malonate were added to 202 parts of biguanide triazine ring are unsubstituted and the products a can be prepared with best yields and simplest procedures. However, the present invention also includes products prepared from substituted biguanides such as phenyl biguanide, allyl biguanide or dimethyl biguanide in which case the correspondingly substituted guanamines are obtained. When substituted biguanides are used the reaction does not proceed as rapidly and as completely and it is sometimes desirable to add a condensing agent such as a metal alkoxide to The products derived from unsubstituted biguanide can usually be prepared without condensing agents but in some cases it may be desirable to accelerate the reaction by the use of a condensing agent.

In general the preferred process of the present invention operates best in the presence of a suitable solvent for the biguanide and/or the ester. I have found that the lower molecular weight alcohols are particularly effective as they are Example 2 Succinoguanaminc (CHzL N and fi-carbomethoxypropionoguanamine Two hundred nine parts of ethyl succinate were added to 101 parts of biguanide dissolved in 400 parts of warm methanol. Within a, few minutes the product began to precipitate from the solution and after standing overnight the product was filtered and washed with methanol. This material was then extracted with about 300 parts of hot ethanol, which dissolved the s-carbomethoxypropionoguanamine melting at 159 C. The residue left from the alcohol extraction was $110- cinoguanamine melting above 335 0.,- which could be further purified by dissolving in warm dilute hydrochloric acid solution, followed by pie-- cipitation with ammonium hydroxide. When the amount of biguanide was doubled the succincguanamine was obtained in about 75% yield and the mono-guanamine was absent.

Example 3 w-carboxypelargonoguanamine C-(CHQBC' O OH i if H1'No C-NH:

One hundred parts of biguanide were added to 280 arts or sodium butyl sebacate'disp'ersed in Twenty parts of w-carboxypelargonoguanamine was dispersed in 200 parts of n-butanol containing 315 parts of sulfuric acid and refluxed for about a'day in'order to effect esterification. The reaction -mixture was neutralized with sodium hydroxide and then extracted with water. After distilling the excess butanol and water, the remaining pasty mass was recrystallized from hot naphtha and then from alcohol by the addition of water until a slight turbidity resulted. The resulting parts of w-carbobutoxypelargonoguanamine was a waxy solid melting at -92 C. and had a saponification equivalent of 323.

Example 5 fi-carboxypropionoguanamine 0CHz"CHz-COH H2NC To 353 parts of biguanide dissolved in about 2500 parts of methanol containing 162 parts of sodium methoxide was added 462 parts of sodium methyl succinate. This reaction mixture was stirred for about one day even though precipitation appeared to be completed in about five to six hours. The insoluble product was removed by filtration and the methanol was concentrated to yield further product. This crude sodium [3- carboxypropionoguanamine amounting to about 425 parts was dissolved in Water, filtered in order to remove the small amount of insoluble material and theneacidified to a pH of about 4.0. The precipitated ,6-carboxypropionoguanamine was filtered, Washed with a large volume of water and then dried at C. The yield of colorless and infusible product was 332 part of 61%.

I claim:

1. A method of making salts of a carboxy polymethylene guanamines which comprises the steps of dissolving a biguanide and a salt of a half ester of a saturated dibas'ic acid in a common solvent whereby reaction between the component is instituted and a precipitate comprising the de'sired salt of the resulting carboxy polymethylene gua namine is formed, continuing the reaction until precipitation substantially ceases, and collecting the precipitated salt of the carboxy polymethylne guanamine.

2. A procedure according to claim 1 in which the biguanide is biguanide.

3. A procedure according to claim 1 in which the solvent is a lower monohydric parafiin alcohol.

4. A process of preparing guanamine polymethylene carboxylic acids which comprises the steps of dissolving a biguanide and 'a salt of a half ester of a saturated dibasic acid in a common solvent whereby reaction is initiated and precipitation is instituted. continuing the reaction until precipitation substantially ceases, collecting the resultant precipitate comprising the desired salt of the carboxy polym'ethylene guanamine, acidifying an aqueous solution of the salt whereby the free guanamine polymethylene carboxylic acid i liberated, and collecting the liberated guanamine polymethylene carboxylic acid.

JACK THEO THURSTON. 

